CN114920891B - Magnetic boron-affinity polyion liquid and preparation method and application thereof - Google Patents
Magnetic boron-affinity polyion liquid and preparation method and application thereof Download PDFInfo
- Publication number
- CN114920891B CN114920891B CN202210527702.XA CN202210527702A CN114920891B CN 114920891 B CN114920891 B CN 114920891B CN 202210527702 A CN202210527702 A CN 202210527702A CN 114920891 B CN114920891 B CN 114920891B
- Authority
- CN
- China
- Prior art keywords
- sio
- affinity
- magnetic
- chlorogenic acid
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
- G01N2021/6421—Measuring at two or more wavelengths
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a preparation method of a magnetic boron affinity polyionic liquid, which comprises the following steps: dispersing 4- (bromomethyl) phenylboronic acid in a solvent, and adding 1-vinylimidazole to react to obtain brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid; fe is added to 3 O 4 Adding nano particles into an alcohol-water system, adding ammonia water and tetraethoxysilane, and performing magnetic field separation after reaction to obtain Fe 3 O 4 @SiO 2 -MPS; fe is added to 3 O 4 @SiO 2 -MPS, deionized water, dilute hydrochloric acid solution and 3- (trimethoxysilyl) propyl methacrylate, and collecting the solid product by external magnetic field to obtain double bond modified Fe 3 O 4 @SiO 2 A microsphere; fe with double bond modified 3 O 4 @SiO 2 Microsphere, brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid, cross-linking agent and initiator, and polymerizing to obtain Fe 3 O 4 @SiO 2 @ PIL. The invention also provides the magnetic boron affinity polyion liquid prepared by the preparation method and application of the magnetic boron affinity polyion liquid in chlorogenic acid detection. Fe provided by the invention 3 O 4 @SiO 2 The @ PIL is simple to prepare, and can realize high selectivity, high sensitivity and rapid detection of trace chlorogenic acid.
Description
Technical Field
The invention relates to the technical field of environmental analysis chemistry, in particular to a magnetic boron affinity polyion liquid and a preparation method and application thereof.
Background
Chlorogenic acid (CGA) is a caffeic acid ester related to quinic acid, one of the most abundant polyphenolic compounds in the human diet. CGA is produced in many fruit crops, such as apples, pears, oranges and coffee. CGA acts as an antioxidant and protects plants from insects and pathogens, as well as prevents enzymatic browning of fruits and vegetables. CGA is also believed to have a number of potential health benefits such as antihypertensive, antimutagenic, antineoplastic, antiobesity, antidiabetic, hypolipidemic, antiinflammatory and antioxidant. In recent years, chlorogenic acid has been widely used in the pharmaceutical industry, foods, and daily chemical industry. Currently, the main methods for determining chlorogenic acid include fluorescence spectrometry, chemiluminescence, chromatography, electrochemical analysis and the like. For example, chinese patent publication No. CN113624863A discloses a method for detecting five chlorogenic acid substances in cowberry fruits by ultra-high performance liquid chromatography-tandem mass spectrometry. Among them, the fluorescence spectrometry has the advantages of fast reaction, low cost, simple operation, etc., and although some fluorescence methods have been applied to CGA detection, it is still required to develop a reliable, fast, simple, sensitive fluorescence detection method.
In recent years, boric acid affinity materials have been rapidly developed and increasingly used in various fields due to the characteristic of selectively separating and enriching molecules containing cis diol. This high affinity interaction makes the boronic acid group a potential affinity ligand for the separation of carbohydrates, nucleotides, nucleic acids, glycoproteins, enzymes and small molecules containing cis-diols (e.g., chlorogenic acid). The magnetic nano material particles have the characteristics of easy preparation, superparamagnetism, low toxicity, good biocompatibility and the like, and the unique superparamagnetism can simply, quickly and efficiently finish the pretreatment operation of complex samples. The carrier used for preparing the traditional boron affinity material has a certain defect, combines the advantages of boron affinity and nano particles, and is used for separating cis-dihydroxyl compounds, thus becoming a research hot spot of scientists. For example, chinese patent publication No. CN104148030A discloses a method for preparing polyethyleneimine modified silica microsphere rich in organic phenylboronic acid. The boron affinity nano material has excellent application prospect in the field of separation analysis due to a simple preparation method and various chemical properties, and is widely used for separating cis-dihydroxy molecules.
Therefore, how to further provide a boron-affinity nanomaterial with higher detection efficiency is a research hotspot in the field.
Disclosure of Invention
The invention aims to provide a preparation method of a magnetic boron affinity polyion liquid, the prepared magnetic boron affinity polyion liquid and application of the magnetic boron affinity polyion liquid in chlorogenic acid detection, and the magnetic boron affinity polyion liquid has the advantages of being strong in specificity and capable of accurately and efficiently detecting chlorogenic acid molecules.
The invention provides the following technical scheme:
a method for preparing a magnetic boron-affinity polyionic liquid, which comprises the following steps:
(1) Dispersing 4- (bromomethyl) phenylboronic acid in a solvent, and adding 1-vinylimidazole to react to obtain brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid;
(2) Fe is added to 3 O 4 Adding nano particles into an alcohol-water system, adding ammonia water and tetraethoxysilane, and performing magnetic field separation after reaction to obtain Fe 3 O 4 @SiO 2 A microsphere; fe is added to 3 O 4 @SiO 2 The microsphere, deionized water, dilute hydrochloric acid solution and 3- (trimethoxysilyl) propyl methacrylate are stirred at room temperature, and solid products are collected through an external magnetic field to obtain the Fe modified with double bonds 3 O 4 @SiO 2 A microsphere;
(3) Fe with double bond modified 3 O 4 @SiO 2 Microsphere, brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazoleDispersing the ionic liquid and the initiator in a solvent, adding a cross-linking agent, and collecting a product through an external magnetic field after the polymerization reaction is completed to obtain the magnetic boron-affinity polyionic liquid Fe 3 O 4 @SiO 2 @PIL。
The magnetic boron-affinity polyionic liquid (Fe 3 O 4 @SiO 2 @pil) combines the boron affinity orientation technique with the advantages of magnetic nanoparticles for the rapid detection of chlorogenic acid, a compound having cis-dihydroxy groups. The method uses double bond modified Fe 3 O 4 @SiO 2 The microsphere is used as a carrier, and the synthesized brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid is added to prepare the magnetic boron affinity polyion liquid material (Fe) capable of rapidly detecting chlorogenic acid by a one-step coprecipitation method 3 O 4 @SiO 2 @ PIL). The magnetic boron-affinity polyionic liquid (Fe 3 O 4 @SiO 2 @ PIL) is simple to prepare, and can realize high selectivity, high sensitivity and rapid detection of trace chlorogenic acid.
Preferably, in step (1), the reaction conditions are: reacting for 18-24 h at 60-90 ℃, wherein the adding mole ratio of the 4- (bromomethyl) phenylboronic acid to the 1-vinyl imidazole is 1:2-1:4.
Preferably, in step (1), the solvent is acetonitrile.
Preferably, in step (2), 200 to 500mg of Fe is used 3 O 4 Preparation of Fe by magnetic nano-particles, 5-10 mL ammonia water and 2-5 mL tetraethoxysilane 3 O 4 @SiO 2 Microsphere, 200-500 mg Fe 3 O 4 @SiO 2 Preparation of double bond modified Fe with 1.0-2.0 mL hydrochloric acid solution with concentration of 0.012mol/l and 0.1-0.5 mL 3- (trimethoxysilyl) propyl methacrylate 3 O 4 @SiO 2 And (3) microspheres.
Preferably, in the step (3), the solvent is acetonitrile, the initiator is ethylene glycol dimethacrylate, and the crosslinking agent is ethylene glycol dimethacrylate.
Preferably, in step (3), 100 to 400mg of Fe modified with double bonds is used 3 O 4 @SiO 2 Particles(s),0.4-0.8 g of brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid, 52mg of azodiisobutyronitrile and 1.3-2.6 g of glycol dimethacrylate.
Preferably, in step (3), the polymerization reaction is carried out at a temperature of 50 to 70℃for a period of 18 to 24 hours.
The invention also provides the magnetic boron-affinity polyion liquid obtained by the preparation method.
The invention also provides application of the magnetic boron affinity polyion liquid in chlorogenic acid detection.
The invention synthesizes polymer Fe by adopting boron affinity nano material 3 O 4 @SiO 2 While the chlorogenic acid itself is fluorescent, the fluorescence intensity in the aqueous solution is weaker along with the decrease of the concentration of the chlorogenic acid, the chlorogenic acid with low concentration in the aqueous solution is difficult to be directly detected by a fluorescence method, and the synthesized polymer can greatly enhance the fluorescence of the chlorogenic acid by adding the synthesized polymer into the chlorogenic acid with low concentration in the aqueous solution. The invention is based on this property and utilizes the synthetic polymer Fe 3 O 4 @SiO 2 The trace chlorogenic acid in the fruits can be detected by the PIL through a fluorometer, and the polymer has the advantages of high selectivity, simplicity, rapidness, high sensitivity and the like for detecting the chlorogenic acid.
Wherein, buffer solution is used for preparing chlorogenic acid standard solution, and magnetic boron affinity polyion liquid Fe is added 3 O 4 @SiO 2 @ PIL, fluorescence detection is performed under shaking or ultrasound.
Preferably, the conditions for detecting the fluorescence value are: excitation wavelength 362nm, voltage 500V. Shaking or ultrasonic treatment for 7min. The PBS buffer had a pH of 6.
In the application of the magnetic boron affinity polyionic liquid in chlorogenic acid detection, the enhanced fluorescence intensity of chlorogenic acid has a good linear relation with the concentration of chlorogenic acid aqueous solution: at a chlorogenic acid concentration of 0.025 μm to 2 μm, the fluorescence intensity and the chlorogenic acid concentration are in line with each other, and the linear equation of the linear standard curve is: y=530.71x+12.7473, where y is the fluorescence intensity at an excitation wavelength of 362nm and a voltage of 500V, and x is the concentration of chlorogenic acid.
The magnetic boron affinity polyionic liquid provided by the invention is formed by combining boron affinity with nano particles, and the fluorescence intensity of chlorogenic acid is greatly enhanced by combining the magnetic boron affinity polyionic liquid with chlorogenic acid with low concentration. Meanwhile, the molecule with cis-dihydroxychlorogenic acid can be more firmly combined and has higher selectivity by utilizing the boron affinity orientation technology. The addition of the magnetic nano material can simply and rapidly complete solid-liquid separation. The polymer has strong anti-interference capability on green antigen detection, high sensitivity, wide linear range and good potential application value.
Drawings
FIG. 1 is Fe 3 O 4 ，Fe 3 O 4 @SiO 2 ，Fe 3 O 4 @SiO 2 -MPS，Fe 3 O 4 @SiO 2 Infrared spectrum of @ PIL.
FIG. 2 is Fe 3 O 4 、Fe 3 O 4 @SiO 2 、Fe 3 O 4 @SiO 2 XRD pattern of @ PIL.
FIG. 3 is Fe 3 O 4 ，Fe 3 O 4 @SiO 2 ，Fe 3 O 4 @SiO 2 -MPS，Fe 3 O 4 @SiO 2 Scanning electron microscope image @ PIL.
FIG. 4 is Fe 3 O 4 @SiO 2 Fluorescence excitation and emission spectra after @ PIL and chlorogenic acid standard solution reaction.
FIG. 5 is Fe 3 O 4 、Fe 3 O 4 @SiO 2 、Fe 3 O 4 @SiO 2 Hysteresis regression curve @ PIL.
FIG. 6 is a graph of Fe at different pH values 3 O 4 @SiO 2 Fluorescence enhancement intensity effect after @ PIL reaction with chlorogenic acid standard.
FIG. 7 is a graph of Fe at various times 3 O 4 @SiO 2 Intensity value of fluorescence enhancement after @ PIL reaction with chlorogenic acid standard solution.
FIG. 8 is Fe 3 O 4 @SiO 2 Fluorescent stack of PIL with chlorogenic acid concentrationAnd (5) adding a graph.
FIG. 9 is Fe 3 O 4 @SiO 2 Linear plot of fluorescence enhancement value of @ PIL as a function of chlorogenic acid concentration versus chlorogenic acid concentration.
FIG. 10 is Fe 3 O 4 、Fe 3 O 4 @SiO 2 、Fe 3 O 4 @SiO 2 @ PIL thermogravimetric analysis.
FIG. 11 is Fe 3 O 4 @SiO 2 Recovery regeneration study of @ PIL.
FIG. 12 is Fe 3 O 4 @SiO 2 The @ PIL detects the fluorescence enhancement of chlorogenic acid and other phenols (1. Mu.M).
FIG. 13 is a structural formula of various phenols.
FIG. 14 is a schematic illustration of the preparation of a magnetic boron-affinity polyionic liquid provided by the present invention.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
As shown in fig. 14, the preparation method of the magnetic boron-affinity polyionic liquid provided in this embodiment includes:
(1) Synthesis of brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid
4- (bromomethyl) phenylboronic acid (10 mmol,2.1485 g) was placed in a 250mL round bottom flask with acetonitrile (80 mL), sonicated for 3 min, then 1-vinylimidazole (40 mmol,3.7648 g) was added dropwise, and the round bottom flask was placed in an 80℃oil bath with stirring and refluxing for 18h. After the reaction is completed, a large amount of anhydrous diethyl ether is added, and white solid is collected after white solid is separated out. Finally, the product is placed in a vacuum drying oven at 60 ℃ and dried for 6 hours to obtain brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid, and the reaction yield is calculated to be 80.9%.
(2) Alkenyl Fe 3 O 4 @SiO 2 Preparation of microspheres
200mg Fe 3 O 4 The magnetic nanoparticles were dispersed in an aqueous alcohol system (100 mL ethanol and 20mL ultra pure water), sonicated for 30min, then 5mL ammonia water was added with stirring, followed by ethyl orthosilicate (2 mL) and the reaction stirred at room temperature for 12h. After the completion of the reaction, the product collected by external magnetic field was washed with deionized water for 6 times and then dried in a vacuum oven at 60℃for 6 hours to obtain Fe 3 O 4 @SiO 2 And (3) microspheres.
200mg of Fe was added to 10mL of ultrapure water 3 O 4 @SiO 2 And dispersed by ultrasonic for 30min, then 1.0mL (0.012 mol/l) of hydrochloric acid solution was added and stirred vigorously, and then 0.1mL of 3- (trimethoxysilyl) propyl methacrylate (TMOPMAS) was added, and the reaction solution was stirred at constant speed at room temperature for 24h. After the reaction was completed, the solid product was collected by an external magnetic field and washed 3 times with ethanol and water, respectively. Finally, drying in vacuum at 60 ℃ for 6 hours to obtain the Fe modified with double bonds 3 O 4 @SiO 2 Microsphere (Fe) 3 O 4 @SiO 2 -MPS)。
(3) Polymer Fe 3 O 4 @SiO 2 Preparation of @ PIL
With alkenyl radicals Fe 3 O 4 @SiO 2 The microsphere is used as a carrier, ethylene glycol dimethacrylate and azodiisobutyronitrile are respectively used as a cross-linking agent and an initiator, and the synthesized brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid and acetonitrile are used as a reaction solvent for free radical polymerization reaction. The specific operation steps are as follows: alkenyl Fe was added sequentially to a 100mL round bottom flask 3 O 4 @SiO 2 Microspheres (100 mg), alkenyl ionic liquid functional monomer (1.29 mmol,0.4 g), and azobisisobutyronitrile (52 mg),ethylene glycol dimethacrylate (6.56 mmol,1.3 g) was finally added with 30mL acetonitrile and dispersed ultrasonically for 10min. After nitrogen is introduced for 30min, the bottle mouth of the round bottom flask is sealed, and the reaction flask is placed in an oil bath pot at 60 ℃ and stirred for 24h at constant temperature. After the reaction was completed, a polymer (Fe) 3 O 4 @SiO 2 @ PIL). Then washing with water and acetonitrile for several times, collecting solid product by external magnetic field, finally drying the polymerization product in vacuum drying oven at 60 deg.C for 6 hr so as to obtain the invented core-shell structured polymer (Fe) 3 O 4 @SiO 2 @PIL)。
(4) Polymer Fe 3 O 4 @SiO 2 Detection of @ PIL
Fluorescence measurements were performed on a Hitachi F-7000 fluorescence spectrophotometer equipped with a 1X 1cm quartz cell, using the following conditions: the excitation and emission slit width was 5nm and the photomultiplier voltage was 500V.
Buffer (prepared by mixing 0.01M NaH with ph=6 2 PO 4 With 0.01M Na 2 HPO 4 Mixing to obtain phosphate buffer solution), preparing chlorogenic acid standard solution, adding 5mg of polymer Fe into 10ml of chlorogenic acid standard solution 3 O 4 @SiO 2 After 7min of oscillation @ PIL the fluorescence intensity was measured at λex/λem=362 nm/461nm at a photomultiplier voltage of 500v. F is chlorogenic acid-containing polymer Fe 3 O 4 @SiO 2 Fluorescence intensity of @ PIL all measurements were performed three times at ambient temperature.
(5) Characterization of materials
FIG. 1 shows Fe 3 O 4 ，Fe 3 O 4 @SiO 2 ，Fe 3 O 4 @SiO 2 -MPS，Fe 3 O 4 @SiO 2 Infrared spectra of @ PIL and brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquids. Characteristic peak 581cm by infrared spectroscopic analysis -1 And 1100cm -1 Fe-O and Si-O-Si, respectively. The stretching vibration peak of C=C appears at 1728cm -1 A place; characteristic peak 1338cm -1 The solution is B-O stretching vibration in brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid. The characteristic peaks can be all in Fe 3 O 4 @SiO 2 The structure of @ PIL is embodied, and successful polymerization of the surface molecular imprinting polyionic liquid is confirmed.
FIG. 2 is Fe 3 O 4 、Fe 3 O 4 @SiO 2 、Fe 3 O 4 @SiO 2 XRD pattern of @ PIL, five major diffraction peaks can be attributed to Fe having inverse spinel structure 3 O 4 Planes in the crystal. The same diffraction peak is observed on the other two composite microspheres, and the crystal structure of the magnetic carrier is not changed by the surface modification of the magnetic carrier, which shows that Fe 3 O 4 Stability of the support and success of surface coating.
FIG. 3 is Fe 3 O 4 ，Fe 3 O 4 @SiO 2 ，Fe 3 O 4 @SiO 2 -MPS，Fe 3 O 4 @SiO 2 Scanning electron microscope image @ PIL.
FIG. 4 is Fe 3 O 4 、Fe 3 O 4 @SiO 2 、Fe 3 O 4 @SiO 2 @ PIL thermogravimetric analysis. Analysis shows that Fe 3 O 4 The surface has minimal quality loss due to no coating; and Fe (Fe) 3 O 4 @SiO 2 The @ PIL has the greatest mass loss due to the greater number of onload. This indicates that in alkenyl Fe 3 O 4 @SiO 2 The surface of the carrier is successfully synthesized into the molecularly imprinted polyionic liquid.
FIG. 5 is Fe 3 O 4 、Fe 3 O 4 @SiO 2 、Fe 3 O 4 @SiO 2 Hysteresis regression curve @ PIL. As shown in FIG. 5, fe 3 O 4 、Fe 3 O 4 @SiO 2 、Fe 3 O 4 @SiO 2 The magnetic properties of the @ PIL sample decrease in turn due to the increasingly more externally coated structures. All three samples showed superparamagnetism at room temperature.
(6) Fluorescence enhancement phenomenon
The chlorogenic acid standard solution shown in FIG. 6 is obtained by adding polymer Fe through fluorescence spectrophotometer exploration 3 O 4 @SiO 2 After @ PIL, the maximum excitation wavelength is 362m, and the maximum emission waveThe length is 461nm. The fluorescence intensity values were different at different pH values, and fig. 7 illustrates that the fluorescence intensity was highest at ph=6. In FIG. 8, the fluorescence intensity was increased with time, and the fluorescence intensity was stabilized at 7min.
(7) Polymer Fe 3 O 4 @SiO 2 @ PIL Performance analysis
Under the optimal conditions, we studied the polymer Fe 3 O 4 @SiO 2 Fluorescence intensity effects of addition of a series of chlorogenic acids at different concentrations to @ PIL. As can be seen from fig. 8, the fluorescence intensity gradually increased with increasing chlorogenic acid concentration. In FIG. 9, polymer Fe 3 O 4 @SiO 2 There is a good linear relationship between the chlorogenic acid concentration of @ PIL in the range of 0.025-2. Mu.M. The linear equation is y=530.71x+12.7473 (R 2 =0.9989, fig. 10).
(8) Recovery regeneration and selectivity exploration
By reacting Fe with 3 O 4 @SiO 2 The recycling and regenerating research of the PIL material is carried out, and the recycling capability of the polymer is examined. As can be seen from FIG. 11, fe 3 O 4 @SiO 2 The @ PIL material can be recycled 5 times, which demonstrates the stability and regeneration capability of the polymer.
By comparing chlorogenic acid with other similar phenols and adding polymer Fe 3 O 4 @SiO 2 The degree of fluorescence enhancement of @ PIL can further verify the selective recognition capability of the polymer. We selected a few phenols as comparison targets, including Caffeic Acid (CA), gallic Acid (GA), vanillic Acid (VA), protocatechuic acid (PCA) (the structural formula is shown in figure 13). As shown in FIG. 12, at the same excitation wavelength, only caffeic acid was added to the polymer Fe 3 O 4 @SiO 2 After @ PIL, the fluorescence intensity was increased, but the fluorescence intensity was lower, while the other phenols showed little increase in fluorescence intensity. Description of the Polymer Fe 3 O 4 @SiO 2 The @ PIL has higher anti-interference performance and can specifically identify chlorogenic acid.
(9) Detection in actual sample
The invention is applicable to actual samples as shown in Table 1The magnetic boron-affinity polyion liquid Fe prepared by the invention is proved 3 O 4 @SiO 2 Feasibility of @ PIL in actual testing can be applied to testing analysis of actual samples.
TABLE 1 detection and recovery of chlorogenic acid in actual samples (n=3)
Claims (10)
1. The preparation method of the magnetic boron-affinity polyionic liquid is characterized by comprising the following steps of:
(1) Dispersing 4- (bromomethyl) phenylboronic acid in a solvent, and adding 1-vinylimidazole to react to obtain brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid;
(2) Fe is added to 3 O 4 Adding nano particles into an alcohol-water system, adding ammonia water and tetraethoxysilane, and performing magnetic field separation after reaction to obtain Fe 3 O 4 @SiO 2 A microsphere; fe is added to 3 O 4 @SiO 2 The microsphere, deionized water, dilute hydrochloric acid solution and 3- (trimethoxysilyl) propyl methacrylate are stirred at room temperature, and solid products are collected through an external magnetic field to obtain the Fe modified with double bonds 3 O 4 @SiO 2 A microsphere;
(3) Fe with double bond modified 3 O 4 @SiO 2 Dispersing microsphere, brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid and initiator in solvent, adding cross-linking agent, and collecting product by external magnetic field after polymerization reaction to obtain magnetic boron affinity polyionic liquid Fe 3 O 4 @SiO 2 @PIL。
2. The method for preparing a magnetic boron-affinity polyionic liquid according to claim 1, wherein in the step (1), the reaction conditions are: reacting for 18-24 h at 60-90 ℃, wherein the adding mole ratio of the 4- (bromomethyl) phenylboronic acid to the 1-vinyl imidazole is 1:2-1:4.
3. The method for preparing a magnetic boron-affinity polyionic liquid according to claim 1, wherein 200-500 mg of Fe is used in the step (2) 3 O 4 Preparation of Fe by magnetic nano-particles, 5-10 mL ammonia water and 2-5 mL tetraethoxysilane 3 O 4 @SiO 2 Microsphere, 200-500 mg Fe 3 O 4 @SiO 2 Preparation of double bond modified Fe with 1.0-2.0 mL hydrochloric acid solution with concentration of 0.012mol/l and 0.1-0.5 mL 3- (trimethoxysilyl) propyl methacrylate 3 O 4 @SiO 2 And (3) microspheres.
4. The method for preparing a magnetic boron-affinity polyionic liquid according to claim 1, wherein 100-400 mg of double-bond modified Fe is used in the step (3) 3 O 4 @SiO 2 The particle, 0.4-0.8 g of brominated 3- (4-benzyl borate) -1-vinyl-1H-imidazole ionic liquid, 52mg of azodiisobutyronitrile and 1.3-2.6 g of ethylene glycol dimethacrylate.
5. The method for preparing a magnetic boron-affinity polyionic liquid according to claim 1, wherein in the step (3), the polymerization reaction is carried out at a temperature of 50-70 ℃ for 18-24 hours.
6. A magnetic boron-affinity polyionic liquid obtained by the method for producing a magnetic boron-affinity polyionic liquid according to any one of claims 1 to 5.
7. Use of the magnetic boron-affinity polyionic liquid according to claim 6 in chlorogenic acid detection.
8. The application of the magnetic boron-affinity polyion liquid in chlorogenic acid detection according to claim 7, wherein a chlorogenic acid standard solution is prepared by using a buffer solution, and the magnetic boron-affinity polyion liquid Fe is added 3 O 4 @SiO 2 @ PIL, fluorescence under shaking or ultrasoundAnd (5) detecting a value.
9. The use of the magnetic boron-affinity polyionic liquid according to claim 8 for chlorogenic acid detection, wherein the fluorescent value detection conditions are: excitation wavelength 362nm, voltage 500V.
10. The use of the magnetic boron affinity polyionic liquid according to claim 8 for chlorogenic acid detection, wherein the concentration of chlorogenic acid is 0.025 μm to 2 μm, the fluorescence intensity and the concentration of chlorogenic acid are in accordance with a linear relationship, and the linear equation of the linear standard curve is: y=530.71x+12.7473, where y is the fluorescence intensity at an excitation wavelength of 362nm and a voltage of 500V, and x is the concentration of chlorogenic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210527702.XA CN114920891B (en) | 2022-05-16 | 2022-05-16 | Magnetic boron-affinity polyion liquid and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210527702.XA CN114920891B (en) | 2022-05-16 | 2022-05-16 | Magnetic boron-affinity polyion liquid and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114920891A CN114920891A (en) | 2022-08-19 |
| CN114920891B true CN114920891B (en) | 2023-08-01 |
Family
ID=82809366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210527702.XA Active CN114920891B (en) | 2022-05-16 | 2022-05-16 | Magnetic boron-affinity polyion liquid and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114920891B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693909A (en) * | 2017-01-19 | 2017-05-24 | 江苏大学 | Phenylboronic acid modified magnetic nanoparticle, and preparation method and application thereof |
| CN111068779A (en) * | 2019-12-16 | 2020-04-28 | 东南大学 | Preparation of noble metal magnetic nano catalyst based on polymerized ionic liquid loading |
| CN111203189A (en) * | 2020-01-22 | 2020-05-29 | 河南工业大学 | PH-responsive magnetic material modified by carboxyl functional polymeric ionic liquid, and preparation method and application thereof |
| CN112110947A (en) * | 2020-09-16 | 2020-12-22 | 陕西科技大学 | Preparation method of ionic liquid modified phenylboronic acid for separating glycoprotein |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2230312A1 (en) * | 2009-03-19 | 2010-09-22 | Helmholtz-Zentrum für Infektionsforschung GmbH | Probe compound for detecting and isolating enzymes and means and methods using the same |
| CN109406473B (en) * | 2018-11-08 | 2019-07-30 | 青岛大学 | A kind of preparation method of phycoerythrin ratio fluorescent sensor |
-
2022
- 2022-05-16 CN CN202210527702.XA patent/CN114920891B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693909A (en) * | 2017-01-19 | 2017-05-24 | 江苏大学 | Phenylboronic acid modified magnetic nanoparticle, and preparation method and application thereof |
| CN111068779A (en) * | 2019-12-16 | 2020-04-28 | 东南大学 | Preparation of noble metal magnetic nano catalyst based on polymerized ionic liquid loading |
| CN111203189A (en) * | 2020-01-22 | 2020-05-29 | 河南工业大学 | PH-responsive magnetic material modified by carboxyl functional polymeric ionic liquid, and preparation method and application thereof |
| CN112110947A (en) * | 2020-09-16 | 2020-12-22 | 陕西科技大学 | Preparation method of ionic liquid modified phenylboronic acid for separating glycoprotein |
Non-Patent Citations (1)
| Title |
|---|
| Rapid and highly selective detection of chlorogenic acid in fruit samples by Fe3O4@SiO2@PIL with boron affinity via a fluorescence enhanced strategy;Tiantian Wan等;New Journal of Chemistry;第2卷(第47期);828-837 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114920891A (en) | 2022-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qian et al. | Si-doped carbon quantum dots: a facile and general preparation strategy, bioimaging application, and multifunctional sensor | |
| Chen et al. | Facile synthesis of nitrogen and sulfur co-doped carbon dots and application for Fe (III) ions detection and cell imaging | |
| Ren et al. | Preparation of molecularly imprinted polymer coated quantum dots to detect nicosulfuron in water samples | |
| CN109180884B (en) | Synthesis and application of nano material for removing patulin | |
| Zhang et al. | Homochiral fluorescence responsive molecularly imprinted polymer: Highly chiral enantiomer resolution and quantitative detection of L-penicillamine | |
| CN104327271B (en) | Molecularly imprinted polymer based on core-shell quantum dot and application thereof | |
| CN101692023B (en) | Chemical preparing method of molecular recognition of ultratrace explosive TNT based on fluorescence resonance energy transfer | |
| CN109021283B (en) | CsPbBr for detecting omethoate3Perovskite quantum dot-molecularly imprinted fluorescent sensor and preparation method thereof | |
| US9201010B2 (en) | Fluorescent organic nanoparticles | |
| CN103160279A (en) | Functional carbon dots, and preparation and application thereof | |
| CN106380619A (en) | Preparation method and application of fluorescent molecularly imprinted adsorption separation material | |
| Liu et al. | A molecularly imprinted polymer placed on the surface of graphene oxide and doped with Mn (II)-doped ZnS quantum dots for selective fluorometric determination of acrylamide | |
| CN108165265B (en) | Water-soluble terbium-doped calcium fluoride nano particle, preparation method and application thereof | |
| Wu et al. | Bimodal counterpropagating-responsive sensing material for the detection of histamine | |
| Qian et al. | Highly sensitive and selective novel core–shell molecularly imprinted polymer based on NaYF4: Yb 3+, Er 3+ upconversion fluorescent nanorods | |
| CN109810281B (en) | Preparation method and application of polymethyl methacrylate nanosphere-based molecularly imprinted fluorescent material | |
| CN114920891B (en) | Magnetic boron-affinity polyion liquid and preparation method and application thereof | |
| Zhu et al. | A selectivity-enhanced fluorescence imprinted sensor based on yellow-emission peptide nanodots for sensitive and visual smart detection of λ-cyhalothrin | |
| Dong-sheng et al. | Preparation, characterization and Hg (II)-sensing behavior of an up-conversion nanocomposite grafted by a rhodamine derived probe: A potential application for eco-industrial park | |
| CN104628945A (en) | Method for preparing ZnS magnetic surface phosphorescent molecularly imprinted polymer | |
| CN109265601B (en) | Nano imprinted microsphere for identifying and fluorescent quantifying pesticide and preparation method thereof | |
| CN108285787B (en) | Method for preparing rare earth fluorescent silica nanoparticles by using microwave heating technology | |
| CN106905696B (en) | A kind of synthetic method of magnetism phosphorescence Microcystin imprinted material | |
| CN110031448A (en) | A kind of nano-stannic oxide/carbon-based point/nano silver surface enhanced Raman substrate preparation method | |
| CN110426377B (en) | Molecularly imprinted polymer material, preparation and application in aspect of detecting epinephrine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |